Copper-Enhanced CO2 Electroreduction in SOECs.

The development of a Co-free and Ni-free electrocatalyst for carbon dioxide electrolysis would be a turning point for the large-scale commercialization of solid-oxide electrolysis cells (CO2-SOECs). Indeed, the demand for cobalt and nickel is expected to become critical by 2050 due to automotive electrification. Currently, the reference materials for CO2-SOEC electrodes are perovskite oxides containing Mn or Co (anodes) and Ni-YSZ cermets (cathodes). However, issues need to be addressed, such as structural degradation and/or carbon deposition at the cathode side, especially at high overpotentials. This work designs the 20 mol % replacement of iron by copper in La0.6Sr0.4FeO3-δ as a multipurpose electrode for CO2-SOECs. La0.6Sr0.4Fe0.8Cu0.2O3-δ (LSFCu) is synthesized by the solution combustion method, and iron partial substitution with copper is evaluated by X-ray powder diffraction with Rietveld refinement, X-ray photoelectron spectroscopy, thermogravimetric analyses, and electrical conductivity assessment. LSFCu is tested as the SOEC anode by measuring the area-specific resistance versus T and pO2. LSFCu structural, electrical, and electrocatalytic properties are also assessed in pure CO2 for the cathodic application. Finally, the proof of concept of a symmetric LSFCu-based CO2-SOEC is tested at 850 °C, revealing a current density value at 1.5 V of 1.22 A/cm2, which is remarkable when compared to similar Ni- or Co-containing systems.

A water cooled, high power, dielectric barrier discharge reactor for CO2 plasma dissociation and valorization studies.

Aiming at the energy efficient use and valorization of carbon dioxide in the framework of decarbonization studies and hydrogen research, a novel dielectric barrier discharge (DBD) reactor has been designed, constructed and developed. This test rig with water cooled electrodes is capable of a plasma power tunable in a wide range from 20W to 2 kW per unit. The reactor was designed to be ready for catalysts and membrane integration aiming at a broad range plasma conditions and processes, including low to moderate high pressures (0.05-2 bar). In this paper, preliminary studies on the highly endothermic dissociation of CO2, into O2 and CO, in a pure, inert, and noble gas mixture flow are presented. These initial experiments were performed in a geometry with a 3 mm plasma gap in a chamber volume of 40cm3, where the process pressure was varied from few 200 mbar to 1 bar, using pure CO2, and diluted in N2. Initial results confirmed the well-known trade-off between conversion rate (up to 60%) and energy efficiency (up to 35%) into the dissociation products, as measured downstream of the reactor system. Improving conversion rate, energy efficiency and the trade-off curve can be further accomplished by tuning the plasma operating parameters (e.g. the gas flow and system geometry). It was found that the combination of a high-power, water-cooled plasma reactor, together with electronic and waveform diagnostic, optical emission and mass spectroscopies provides a convenient experimental framework for studies on the chemical storage of fast electric power transients and surges.

Cobalt Oxide Synthesis via Flame Spray Pyrolysis as Anode Electrocatalyst for Alkaline Membrane Water Electrolyzer.

Nanostructured cobalt oxide powders as electro catalysts for the oxygen evolution reaction (OER) in an alkaline membrane electrolysis cell (AME) were prepared by flame spray synthesis (FS); an AME's anode was then produced by depositing the FS prepared cobalt oxide powders on an AISI-316 sintered metal fiber by the electrophoretic deposition (EPD) method. FS powders and the composite electrode were characterized by SEM, XRD, and XPS analysis. The electrode showed an increase in the OER catalytic activity in a KOH 0.5 M solution with respect to commercial materials commonly applied in alkaline electrolysis, demonstrating that the flame spray synthesis of nanoparticles combined with the electrophoretic deposition technique represent an effective methodology for producing an anodic catalyst for alkaline membrane electrolyzers.

Towards Perfect Absorption of Single Layer CVD Graphene in an Optical Resonant Cavity: Challenges and Experimental Achievements.

Graphene is emerging as a promising material for the integration in the most common Si platform, capable to convey some of its unique properties to fabricate novel photonic and optoelectronic devices. For many real functions and devices however, graphene absorption is too low and must be enhanced. Among strategies, the use of an optical resonant cavity was recently proposed, and graphene absorption enhancement was demonstrated, both, by theoretical and experimental studies. This paper summarizes our recent progress in graphene absorption enhancement by means of Si/SiO2-based Fabry-Perot filters fabricated by radiofrequency sputtering. Simulations and experimental achievements carried out during more than two years of investigations are reported here, detailing the technical expedients that were necessary to increase the single layer CVD graphene absorption first to 39% and then up to 84%. Graphene absorption increased when an asymmetric Fabry-Perot filter was applied rather than a symmetric one, and a further absorption increase was obtained when graphene was embedded in a reflective rather than a transmissive Fabry-Perot filter. Moreover, the effect of the incident angle of the electromagnetic radiation and of the polarization of the light was investigated in the case of the optimized reflective Fabry-Perot filter. Experimental challenges and precautions to avoid evaporation or sputtering induced damage on the graphene layers are described as well, disclosing some experimental procedures that may help other researchers to embed graphene inside PVD grown materials with minimal alterations.

Tuning the Electronic Properties of Graphane via Hydroxylation: An Ab Initio Study.

The thermodynamic stability of hydroxylated graphane, that is, fully sp3 graphene derivatives coordinated with -H and -OH groups, has been recently demonstrated by ab initio calculations. Within the density functional theory approach, we investigate the electronic property modifications of graphane by progressive hydroxylation, that is, by progressively substituting -H with -OH groups. When 50% of graphane is hydroxylated, the energy bandgap reaches its largest value of 6.68 eV. The electronic affinity of 0.8 eV for graphane can widely change in the 0.28-1.60 eV range depending on the geometric configuration. Hydroxylated graphane has two interfaces with vacuum, hence its electron affinity can be different on each interface with the formation of an intrinsic dipole perpendicular to the monolayer. We envisage the possibility of using hydroxylated graphane allotropes with tunable electronic affinity to serve as interfacial layers in 2D material-based heterojunctions.

A three-dimensional nerve guide conduit based on graphene foam/polycaprolactone.

In this study, a novel nerve guide conduit was developed, based on a three-dimensional (3D) graphene conductive core grown, by chemical vapor deposition (CVD) coupled with a polycaprolactone (PCL) polymer coating. Firstly, the monolithic 3D-graphene foam (3D-GF) was synthesized on Ni foam templates via inductive heating CVD, subsequently, Ni/Graphene samples were dipped successively in PCL and cyclododecane (CDD) solutions prior to the removal of Ni from the 3D-GF/PCL scaffold in FeCl3. Our results showed that the electrical conductivity of the polymer composites reached to 25 S.m-1 after incorporation of 3D-GF. Moreover, the mechanical properties of 3D-GF/PCL composite scaffold were enhanced with respect to the same geometry of PCL scaffolds. The wettability, surface porosity, and morphology did not show any significant changes, while the PC12 cell proliferation and extension were increased for the developed 3D-GF/PCL nanocomposite. It can be concluded that 3D-GF/PCL nanocomposites could be good candidates to utilize as a versatile system for the engineering of peripheral nerve tissue.

Experimental demonstration of mid-IR absorption enhancement in single layer CVD graphene.

Mid-IR absorption of single layer graphene (SLG) was simulated and experimentally demonstrated by embedding a SLG grown by chemical vapor deposition (CVD) inside a Fabry-Perot (FP) filter made by alternating quarter wave Si and SiO2 layers fabricated by radiofrequency sputtering. The absorption from the graphene layer was modeled by using COMSOL Multiphysics in four different configurations, depending on its position inside the filter, an asymmetric FP made of two different dielectric mirrors separated by a cavity. In the first three configurations, graphene was inserted at the center of the optical cavity and inside the top or bottom dielectric mirror forming the FP. The fourth configuration involves two layers of graphene, each positioned inside one of the dielectric mirrors. The calculated electric field distribution inside the FP shows two symmetric maxima just above and below the cavity, i.e., inside the mirrors, while the electric field at the center of the cavity is negligible. For the experimental demonstration, the graphene geometry corresponding to the maximum electric field intensity was chosen, and, between two equivalent alternatives, the one with the easiest fabrication procedure was selected. Results demonstrate a maximum experimental absorption of 50% at 4342 nm for SLG when inserted in the top mirror of the FP, in excellent agreement with the simulated value of 53%.

A novel water-resistant and thermally stable black lead halide perovskite, phenyl viologen lead iodide C22H18N2(PbI3)2.

A novel black organoammonium iodoplumbate semiconductor, namely phenyl viologen lead iodide C22H18N2(PbI3)2 (PhVPI), was successfully synthesized and characterized. This material showed physical and chemical properties suitable for photovoltaic applications. Indeed, low direct allowed band gap energy (Eg = 1.32 eV) and high thermal stability (up to at least 300 °C) compared to methylammonium lead iodide CH3NH3PbI3 (MAPI, Eg = 1.5 eV) render PhVPI potentially attractive for solar cell fabrication. The compound was extensively characterized by means of X-ray diffraction (performed on both powder and single crystals), UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS), UV-photoelectron spectroscopy (UPS), FT-IR spectroscopy, TG-DTA, and CHNS analysis. Reactivity towards water was monitored through X-ray powder diffraction carried out after prolonged immersion of the material in water at room temperature. Unlike its methyl ammonium counterpart, PhVPI proved to be unaffected by water exposure. The lack of reactivity towards water is to be attributed to the quaternary nature of the nitrogen atoms of the phenyl viologen units that prevents the formation of acid-base equilibria when in contact with water. On the other hand, PhVPI's thermal stability was evaluated by temperature-controlled powder XRD measurements following an hour-long isothermal treatment at 250 and 300 °C. In both cases no signs of decomposition could be detected. However, the compound melted incongruently at 332 °C producing, upon cooling, a mostly amorphous material. PhVPI was found to be slightly soluble in DMF (∼5 mM) and highly soluble in DMSO. Nevertheless, its solubility in DMF can be dramatically increased by adding an equimolar amount of DMSO. Therefore, phenyl viologen lead iodide can be amenable for the fabrication of solar devices by spin coating as actually done for MAPI-based cells. The crystal structure, determined by means of single crystal X-ray diffraction using synchrotron radiation, turned out to be triclinic and consequently differs from the prototypal perovskite structure. In fact, it comprises infinite double chains of corner-sharing PbI6 octahedra along the a-axis direction with phenyl viologen cations positioned between the columns. Finally, the present determination of PhVPI's electronic band structure achieved through UPS and UV-Vis DRS is instrumental in using the material for solar cells.

Experimental near infrared absorption enhancement of graphene layers in an optical resonant cavity.

Graphene has recently emerged as a promising candidate for a wide range of photonic and optoelectronic applications, with a high application potential in devices using infrared radiation. The optical absorption of 2D materials and graphene can be uniquely enhanced when they are embedded in optical resonant cavities, since optically-thin atomic-thickness absorbers do not perturb the cavity itself. Despite the many theoretical studies, experimental validation is still lagging behind. Here, large near infrared (NIR) absorption of unpatterned chemical vapor deposition graphene is experimentally demonstrated for the first time in a large area (1 inch) passive optical device by exploiting the enhancement of the electric field at the center of a Fabry-Perot cavity. Test devices were fabricated with single layer, double layer and five layers graphene, sandwiched between two almost symmetric Bragg mirrors deposited by radio frequency sputtering and consisting of alternate layers of Si and SiO2. A thin evaporated MgF2 overlayer was used to reduce sputtering induced damage on graphene layers. Measured absorption values, in the range of 37%-45%, were found in very good accordance with simulated ones. A maximum absorption of 45% was measured at 2345 nm for the double-layer graphene.

Electronic and optical properties of metal decorated nitrogen-doped vacancy defects in graphene.

We present a first principles study of the stability, and of the electronic and optical properties of graphene with nitrogen doped vacancies. Moreover, we use the vacancies as anchoring sites for Mg, Zn, Pd al Pt atoms and vary the concentration of defects. Decoration of the defects with metal atoms produces semi-metallic systems for any studied size of the cell, with linear bands crossing at the Fermi level. The peculiar electronic properties of massless Dirac fermions in graphene are hence kept, although with anisotropic Fermi velocities. New sharp peaks appear in the optical conductivity in the visible range, thus strongly enhancing the optical response of graphene.

Electrochemical synthesis of self-organized TiO2 crystalline nanotubes without annealing.

This work demonstrates that upon anodic polarization in an aqueous fluoride-containing electrolyte, TiO2 nanotube array films can be formed with a well-defined crystalline phase, rather than an amorphous one. The crystalline phase was obtained avoiding any high temperature annealing. We studied the formation of nanotubes in an HF/H2O medium and the development of crystalline grains on the nanotube wall, and we found a facile way to achieve crystalline TiO2 nanotube arrays through a one-step anodization. The crystallinity of the film was influenced by the synthesis parameters, and the optimization of the electrolyte composition and anodization conditions (applied voltage and time) were carried out. For comparison purposes, crystalline anatase TiO2 nanotubes were also prepared by thermal treatment of amorphous nanotubes grown in an organic bath (ethylene glycol/NH4F/H2O). The morphology and the crystallinity of the nanotubes were studied by field emission gun-scanning electron microscopy (FEG-SEM) and Raman spectroscopy, whereas the electrochemical and semiconducting properties were analyzed by means of linear sweep voltammetry, impedance spectroscopy, and Mott-Schottky plots. X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS) allowed us to determine the surface composition and the electronic structure of the samples and to correlate them with the electrochemical data. The optimal conditions to achieve a crystalline phase with high donor concentration are defined.

Contamination-free graphene by chemical vapor deposition in quartz furnaces.

Although the growth of graphene by chemical vapor deposition is a production technique that guarantees high crystallinity and superior electronic properties on large areas, it is still a challenge for manufacturers to efficiently scale up the production to the industrial scale. In this context, issues related to the purity and reproducibility of the graphene batches exist and need to be tackled. When graphene is grown in quartz furnaces, in particular, it is common to end up with samples contaminated by heterogeneous particles, which alter the growth mechanism and affect graphene's properties. In this paper, we fully unveil the source of such contaminations and explain how they create during the growth process. We further propose a modification of the widely used quartz furnace configuration to fully suppress the sample contamination and obtain identical and clean graphene batches on large areas.

An ab initio study of hydroxylated graphane.

Graphene-based derivatives with covalent functionalization and well-defined stoichiometry are highly desirable in view of their application as functional surfaces. Here, we have evaluated by ab initio calculations the energy of formation and the phase diagram of hydroxylated graphane structures, i.e., fully functionalized graphene derivatives coordinated with -H and -OH groups. We compared these structures to different hydrogenated and non-hydrogenated graphene oxide derivatives, with high level of epoxide and hydroxyl groups functionalization. Based on our calculations, stable phases of hydroxylated graphane with low and high contents of hydrogen are demonstrated for high oxygen and hydrogen partial pressure, respectively. Stable phases of graphene oxide with a mixed carbon hybridization are also found. Notably, the synthesis of hydroxylated graphane has been recently reported in the literature.

Chemical Vapor Deposited Graphene-Based Derivative As High-Performance Hole Transport Material for Organic Photovoltaics.

The development of efficient charge transport layers is a key requirement for the fabrication of efficient and stable organic solar cells. A graphene-based derivative with planar resistivity exceeding 10(5) Ω/□ and work function of 4.9 eV is here produced by finely tuning the parameters of the chemical vapor deposition process on copper. After the growth, the film is transferred to glass/indium tin oxide and used as hole transport layer in organic solar cells based on a PBDTTT-C-T:[70]PCBM blend. The cells attained a maximum power conversion efficiency of 5%, matching reference cells made with state-of-the-art PEDOT: PSS as the hole transport layer. Our results indicate that functionalized graphene could represent an effective alternative to PEDOT: PSS as hole transport/electron blocking layer in solution-processed organic photovoltaics.

Nitrogen-doped graphene films from chemical vapor deposition of pyridine: influence of process parameters on the electrical and optical properties.

Graphene films were produced by chemical vapor deposition (CVD) of pyridine on copper substrates. Pyridine-CVD is expected to lead to doped graphene by the insertion of nitrogen atoms in the growing sp(2) carbon lattice, possibly improving the properties of graphene as a transparent conductive film. We here report on the influence that the CVD parameters (i.e., temperature and gas flow) have on the morphology, transmittance, and electrical conductivity of the graphene films grown with pyridine. A temperature range between 930 and 1070 °C was explored and the results were compared to those of pristine graphene grown by ethanol-CVD under the same process conditions. The films were characterized by atomic force microscopy, Raman and X-ray photoemission spectroscopy. The optical transmittance and electrical conductivity of the films were measured to evaluate their performance as transparent conductive electrodes. Graphene films grown by pyridine reached an electrical conductivity of 14.3 × 10(5) S/m. Such a high conductivity seems to be associated with the electronic doping induced by substitutional nitrogen atoms. In particular, at 930 °C the nitrogen/carbon ratio of pyridine-grown graphene reaches 3%, and its electrical conductivity is 40% higher than that of pristine graphene grown from ethanol-CVD.